KR101973137B1 - Conductive adhesive composition - Google Patents

Abstract

An epoxy resin, and an electrically conductive filler; and a urethane resin having an average particle diameter of 4 탆 or more and 13 탆 or less and an A-type durometer hardness of 55 to 90 as measured according to JIS K 6253 There is provided a conductive adhesive composition containing resin particles.

Description

Conductive adhesive composition

The present invention relates to a conductive adhesive composition for use in a printed wiring board.

Conventionally, a conductive adhesive in which a conductive filler is added to an adhesive resin composition is used for bonding a reinforcing plate or an electromagnetic wave shielding film to a printed wiring board. When the reinforcing plate or the electromagnetic wave shielding film is adhered to the printed wiring board, an opening is formed in the cover rail of the printed wiring board to expose a circuit made of copper foil or the like, and the opening is filled with a conductive adhesive, The electromagnetic wave shielding film is electrically connected.

As such a conductive adhesive, for example, an adhesive in which a conductive filler and silica particles having a predetermined specific surface area are mixed with a thermosetting resin has been disclosed. It has been described that by blending such silica particles, the damage of the insulating layer can be suppressed without deteriorating the flexibility of the entire electromagnetic wave shielding film (see, for example, Patent Document 1). Also disclosed is an adhesive sheet comprising a polyurethane polyurea resin having a predetermined acid value and an adhesive composition containing an epoxy resin. Further, it is described that reflow-resistant property is improved by using such an adhesive sheet (see, for example, Patent Document 2).

Japanese Patent Application Laid-Open No. 2015-53412 Japanese Patent No. 4806944

In general, when the conductive adhesive is subjected to a reflow process (for example, at 270 DEG C for 10 seconds), conductivity and adhesiveness to a printed wiring board are lowered. Therefore, the flowability of the conductive adhesive (which can withstand the reflow process High heat resistance and conductivity after the reflow process and high adhesiveness to the printed wiring board) are required. In addition, recently, the electronic substrate tends to be miniaturized, and the hole diameter of the opening formed in the coverlay tends to be reduced.

However, in the adhesive described in Patent Document 1, when the silica particles are added, the ratio of the thermosetting resin is lowered, so that there is a problem that the adhesiveness with the reinforcing plate or the printed wiring board is deteriorated.

Further, in the adhesive sheet described in Patent Document 2, since the connection resistance value is increased when the adhesive composition is filled in the opening of the coverlay and then subjected to the reflow process, there is a problem that the flowability is insufficient.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a conductive adhesive composition capable of securing excellent conductivity and adhesion to a printed wiring board even after reflowing.

In order to achieve the above object, the conductive adhesive composition of the present invention comprises a thermosetting resin having a functional group capable of reacting with an epoxy group, an epoxy resin, and an electrically conductive filler and having an average particle diameter of 4 탆 to 13 탆, (Type A) durometer hardness of not less than 55 but not more than 90, which is measured in accordance with ASTM D-6253.

According to the present invention, it is possible to provide a conductive adhesive composition having excellent conductivity and adhesion to a printed wiring board even after reflowing.

1 is a sectional view of a conductive adhesive film according to an embodiment of the present invention.
2 is a cross-sectional view of a shielded printed wiring board according to an embodiment of the present invention.
3 is a cross-sectional view of a shielded printed wiring board according to an embodiment of the present invention.
4 is a cross-sectional view of a shielded printed wiring board according to an embodiment of the present invention.
5 is a cross-sectional view of a flexible substrate used in the embodiment.
6 is a diagram for explaining a method of measuring the electric resistance value in the embodiment.

Hereinafter, the conductive adhesive composition of the present invention will be specifically described. The present invention is not limited to the following embodiments, but can be appropriately modified and applied without departing from the gist of the present invention.

The conductive adhesive composition of the present invention is a conductive adhesive composition comprising a thermosetting resin, a conductive filler (H) and a urethane resin particle (I).

The thermosetting resin is not particularly limited and a polyamide resin, a polyimide resin, an acrylic resin, a phenol resin, an epoxy resin, a polyurethane resin, a polyurethaneurea resin, a melamine resin and an alkyd resin can be used have. These may be used alone or in combination of two or more. Among them, the thermosetting resin is preferably a thermosetting resin having a functional group capable of reacting with an epoxy group, from the viewpoint of obtaining excellent bottom flowability. Examples of such thermosetting resins include epoxy group modified polyester resins, epoxy group modified polyamide resins, epoxy group modified acrylic resins, epoxy group modified polyurethane polyurea resins, carboxyl group modified polyester resins, carboxyl group modified polyamide resins, Resin, a carboxyl group-modified polyurethane polyurea resin, and the like. Among these, a carboxyl group-modified polyester resin, a carboxyl group-modified polyamide resin and a carboxyl group-modified polyurethane polyurea resin are preferable.

When the thermosetting resin is a carboxyl group-modified thermosetting resin, the acid value thereof is preferably 2 to 100 mgKOH / g, more preferably 2 to 50 mgKOH / g, and even more preferably 3 to 30 mgKOH / g. When the acid value is 2 mgKOH / g or more, the epoxy resin is sufficiently cured with the epoxy resin described later, so that the heat resistance of the conductive adhesive composition is improved. When the acid value is 100 mgKOH / g or less, the epoxy resin sufficiently cures with the epoxy resin described later, so that the peel strength of the conductive adhesive composition becomes good.

(Carboxyl group modified polyester resin)

The carboxyl group-modified polyester resin can be obtained, for example, by reacting a hydroxyl group-containing polyester resin with a polybasic acid having three or more carboxyl groups in the molecule or an anhydride thereof.

The hydroxyl group-containing polyester resin can be obtained by reacting a diol with a dibasic acid or a dibasic acid anhydride or a dialkyl ester of a dibasic acid.

The diols are, for example, diols of linear or branched aliphatic compounds having 2 to 12 carbon atoms, specifically, ethylene glycol, diethylene glycol, propylene glycol ), Neopentyl glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-n-butyl-2-ethyl-1,3-propane di Trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-diethyl-1,3-propanediol, 1,9 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexane dimethanol, or 3-methyl- , 5-pentanediol, or a diol of an aromatic compound having 6 to 15 carbon atoms, specifically bisphenol A or bisphenol F Divalent aliphatic, such as alkylene oxide (ethylene oxide) or to the addition of propylene oxide (propylene oxide), hexylene glycol (hexylene glycol), hydrogenated bisphenol A and the like can be mentioned alcohols (aliphatic dihydric alcohol).

Examples of the dibasic acid or dibasic acid anhydride which reacts with the diol include an aromatic dicarboxylic acid, an aliphatic cyclic dicarboxylic acid, an aliphatic dicarboxylic acid, and anhydrides thereof.

The aromatic dicarboxylic acid or its anhydride includes, for example, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid, or (anhydrous) phthalic acid. Herein, for example, " (anhydrous) phthalic acid " collectively means phthalic acid and phthalic anhydride.

Examples of the aliphatic cyclic dicarboxylic acid or its anhydride include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, and the like. Examples of the aliphatic dicarboxylic acid or its anhydride include succinic acid, fumaric acid, (anhydrous) maleic acid, adipic acid, sebacic acid, azelaic acid ), And hy- phamic acid.

As the dialkyl ester of the dibasic acid to be reacted with the diol, for example, there can be mentioned an ester of the dibasic acid and the linear or branched alkyl alcohol having 1 to 18 carbon atoms. Examples of the linear or branched alkyl alcohol having 1 to 18 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert- n-amyl alcohol, acetyl isopropyl alcohol, neohexyl alcohol, isohexyl alcohol, n-hexyl alcohol, heptyl alcohol, octyl alcohol, decyl alcohol ), Dodecyl alcohol, or octadecyl alcohol.

Preferred compounds as dialkyl esters of dibasic acids are dimethyl phthalic acid and dimethyl isophthalic acid.

The carboxyl group-containing polyester resin can be obtained by reacting a polyester resin having a hydroxyl group with a polybasic acid or an anhydride thereof having three or more (preferably three or four) carboxyl groups in the molecule.

Examples of the polybasic acid or its anhydride having three or more carboxyl groups in the molecule include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, or ethylene glycol bistrimellitate dianhydride.

(Carboxyl group modified polyamide resin)

The carboxyl group-modified polyamide resin is synthesized by a condensation reaction from a polyvalent carboxylic acid component such as a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid dianhydride and the like, an organic diisocyanate or a diamine.

Examples of the polyvalent carboxylic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, dimer acid, etc. Aromatic dicarboxylic acids such as aliphatic dicarboxylic acid, isophthalic acid, terephthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenylsulfon dicarboxylic acid and oxydibenzoic acid, trimellitic acid, pyromellitic acid, Aromatic carboxylic acid anhydrides such as diphenylsulfone tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride, and the like. These may be used alone or in combination of two or more.

Examples of the organic diisocyanate include 4,4'-diphenyl methane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate An aromatic diisocyanate such as m-xylene diisocyanate and m-tetramethyl xylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexa But are not limited to, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane- 1,4-diisocyanate, hydrogenated m-xylene di And aliphatic isocyanates such as isocyanate, lysine diisocyanate and the like. These may be used alone or in combination of two or more.

Instead of the organic diisocyanate, a diamine may also be used. Examples of diamines include phenylenediamine, diaminodiphenylpropane, diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, Diaminodiphenyl sulfide, diaminodiphenyl ether, and the like.

(Carboxyl group-modified polyurethane polyurea resin)

The carboxyl group-modified polyurethane polyurea resin is preferably a polyurethane polyurea resin (F) obtained by reacting a urethane prepolymer (D) with a polyamino compound (E). Here, the urethane prepolymer (D) is obtained by reacting a polyol compound (A), a diisocyanate compound (B) and a diol compound (C) having a carboxyl group.

≪ Polyol Compound (A) >

The polyol compound of the present invention is not particularly limited, and a known polyol used for urethane synthesis can be used. Such polyols include, for example, polyester polyols, polyether polyols, polycarbonate polyols, and other polyols.

Examples of the polyester polyol include aliphatic dicarboxylic acids (e.g., succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.) and / or aromatic dicarboxylic acids (e.g., isophthalic acid, terephthalic acid, And low molecular weight glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, 1,4 -Bis hydroxymethylcyclohexane) and the like.

Specific examples of such polyester polyols include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, poly neopentyl adipate diol, polyethylene / butylene Adipate diol, poly neopentyl / hexyl adipate diol, poly-3-methylpentane adipate diol, polybutylene isophthalate diol, polycaprolactone diol, poly-3-methyl Valerolactone diol, and the like.

Specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random / block copolymers thereof. Specific examples of the polycarbonate polyol include polytetramethylene carbonate diol, polypentamethylene carbonate diol, poly neopentyl carbonate diol, polyhexamethylene carbonate diol, poly (1,4-cyclohexane dimethylene carbonate) Diols, and random / block copolymers thereof.

Specific examples of the other polyols include dimer diol, polybutadiene polyol and its hydrogenated product, polyisoprene polyol and its hydrogenated product, acrylic polyol, epoxy polyol, polyether ester polyol, Siloxane-modified polyol,?,? - polymethyl methacrylate diol,?,? - polyditmethacrylate diol, and the like.

The number average molecular weight (Mn, determined by terminal functional group amount) of the polyol compound (A) is not particularly limited, but is preferably 500 to 3,000. When the number average molecular weight (Mn) of the polyol compound (A) is less than 500, the cohesive force of the urethane bond is difficult to manifest and mechanical properties tend to be lowered. In addition, the crystalline polyol having a number average molecular weight of more than 3,000 may cause whitening when it is formed into a film. The polyol compound (A) may be used alone or in combination of two or more.

As the reaction component for obtaining the urethane prepolymer (D), it is also preferable to use a short chain diol component and / or a diamine component if necessary. This makes it easy to control the hardness, viscosity (viscosity) and the like of the polyurethane polyurea resin (F). Specific examples of the short chain diol component include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, And an alkylene oxide moiety adduct (number average molecular weight less than 500 by terminal functional group quantitation); Aliphatic cyclic glycols such as 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexane dimethanol, and alkylene oxide low-molecular adducts thereof (number average molecular weight less than 500, homology); Aromatic glycols such as xylylene glycol and their alkylene oxide adducts (number average molecular weight less than 500, homology); Bisphenols such as bisphenol A, thiobisphenol, and sulfone bisphenol, and alkylene oxide adducts thereof (number average molecular weight less than 500, homology); Alkyl dialkanol amines such as C1-C18 alkyl diethanol amines and the like.

Specific examples of the diamine compound include short chain aliphatic diamine compounds such as methylene diamine, ethylenediamine, trimethylenediamine, hexamethylenediamine, and octamethylenediamine; Phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis (phenylamine), 4,4'-diaminodiphenyl ether, Aromatic diamine compounds such as 4'-diaminodiphenly sulfone; Aliphatic cyclic diamine compounds such as cyclopentyldiamine, cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane and isophoronediamine, and the like can be given . In addition, hydrazines such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebas soda iodazide, phthalic acid dihydrazide, and the like may be used as the diamine It can be used as a minor compound. Examples of the long chain include long-chain alkylene diamines, polyoxyalkylene diamines, terminal amine polyamides, and siloxane-modified polyamines. These diamine compounds may be used alone or in combination of two or more.

≪ Diisocyanate compound (B) >

The diisocyanate compound (B) of the present invention is not particularly limited, but conventionally known diisocyanate compounds used in the production of polyurethane can be used. Specific examples of the diisocyanate compound (B) include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl- , 3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4- Cyanate diphenyl ether, 4,4'-methylene bis (phenylene isocyanate) (MDI), durylene diisocyanate, tolyldinedisocyanate, xylylene diisocyanate Aromatic diisocyanates such as benzene dianhydride, benzene dianisocyanate, o-nitrobenzene diisocyanate, and 4,4'-diisocyanate biphenyl, such as benzene dianhydride (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, Diisocyanate; Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; ; 1,4-cyclohexylene diisocyanate, methylene bis (4-cyclohexylisocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophoronediisocyanate, hydrogenated MDI , Aliphatic cyclic diisocyanates such as hydrogenated XDI; And polyurethane prepolymers obtained by reacting these diisocyanates with low molecular weight polyols or polyamines so that the terminals become isocyanates.

<Diol compound (C) having a carboxyl group>

The diol compound (C) having a carboxyl group of the present invention is not particularly limited, and examples thereof include dimethylol alkanoic acid such as dimethylol propionic acid and dimethylol butyric acid; Alkylene oxide adduct of dimethylolalkanoic acid (number average molecular weight less than 500 by terminal functional group quantitation); Epsilon -caprolactone adduct of dimethylolalkanoic acid (number-average molecular weight less than 500 by terminal functional group quantitation); Half-esters derived from acid anhydride of dimethylolalkanoic acid and glycerin; A compound obtained by free radical reaction of a hydroxyl group of dimethylolalkanoic acid, a monomer having an unsaturated bond, and a monomer having a carboxyl group and an unsaturated bond. Of these, dimethylol propionic acid and dimethylol alkanoic acid such as dimethylol butyric acid are readily available, and the acid value can be easily adjusted.

&Lt; Urethane prepolymer (D) >

The urethane prepolymer (D) of the present invention is obtained by reacting the aforementioned polyol compound (A), diisocyanate compound (B) and diol compound (C) having a carboxyl group.

In the reaction, the equivalent ratio of the polyol compound (A) to the diisocyanate compound (B) relative to the hydroxyl group of the diol compound (C) having a carboxyl group is preferably 1.1 to 2.5. Within the above range, a conductive adhesive composition having high heat resistance and mechanical strength can be obtained. The reaction temperature is not particularly limited, but the reaction is carried out at 60 to 100 占 폚.

&Lt; Reaction terminator >

When the urethane prepolymer (D) is obtained by reacting the polyol compound (A), the diisocyanate compound (B) and the diol compound (C) having a carboxyl group for the purpose of adjusting the molecular weight of the urethane prepolymer, Can be used. As the reaction terminator, a monoalcohol compound, a monoamine compound, an alkanolamine compound, or the like can be used. As the monoalcohol, for example, methanol, ethanol, butanol, isopropanol and the like can be used. As the monoamine compound, butylamine, dibutylamine and the like can be used. As the alkanolamine, monoethanolamine, diethanolamine and the like can be used.

&Lt; Polyamino compound (E) >

The polyamino compound (E) of the present invention is not particularly limited, and conventionally known polyamino compounds used for producing a polyurea resin can be used. Specific examples of the polyamino compound (E) include ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'- Dicyclohexylmethanediamine, dicyclohexylmethindiamine, 3,3'-dimethyl-4,4'-dicyclohexylmethindiamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 1 , 2-propanediamine, and the like; And aminoalkylalkanolamines such as aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine, aminopropylpropanolamine, aminohexylpropanolamine, and the like.

&Lt; Polyurethane polyurea resin (F) >

The weight average molecular weight of the polyurethane polyurea resin (F) of the present invention is usually 50,000 to 100,000.

&Lt; Epoxy resin &

The epoxy resin of the present invention is not particularly limited, and a known epoxy resin having two or more epoxy groups per molecule can be used. Examples of such epoxy resins include bisphenol-type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins and bisphenol S type epoxy resins, spirocyclic epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins Glycidyl ether type epoxy resins such as epoxy resin, terpene type epoxy resin, tris (glycidyloxyphenyl) methane and tetrakis (glycidyloxyphenyl) ethane, tetraglycidyldiaminodiphenylmethane and the like Phenol novolak type epoxy resin,? -Naphthol novolak type epoxy resin, and brominated phenol novolac type epoxy resin, and the like, and the like, for example, epoxy resins such as glycidylamine type epoxy resin, tetrabromobisphenol A type epoxy resin, cresol novolak type epoxy resin, Novolak-type epoxy resins, and rubber-modified epoxy resins. These may be used alone, or two or more of them may be mixed.

The epoxy equivalent of the epoxy resin is preferably 800 to 100000. This is preferable in that the adhesion with the reinforcing plate is further improved.

When two or more kinds of epoxy resins are used in combination, an epoxy resin having an epoxy equivalent of 800 to 10,000 and an epoxy resin having an epoxy equivalent of 90 to 300 are preferably used in combination. In this case, the epoxy resin having an epoxy equivalent of 800 to 10000 and the epoxy resin having an epoxy equivalent of 90 to 300 may be of the same kind or of different chemical structures.

The epoxy resin having an epoxy equivalent of 800 to 10000 is preferable because adhesion with the reinforcing plate is further improved. The lower limit of the epoxy equivalent is more preferably 1000, and still more preferably 1500. The upper limit of the epoxy equivalent is more preferably 5000, and still more preferably 3000. As the epoxy resin having an epoxy equivalent of 800 to 10,000, it is preferable to use a resin which is solid at room temperature. A solid at room temperature means a solid state having no fluidity at 25 DEG C in a solventless state.

EPICLON 4050, 7050, HM-091, and HM-101 (trade names, manufactured by DIC Corporation), jER1003F, 1004, 1004AF, 1004FS, 1005F, and 1005F are commercially available epoxy resins that can be used as an epoxy resin having an epoxy equivalent of 800 to 10,000. 1006FS, 1007, 1007FS, 1009, 1009F, 1010, 1055, 1256, 4250, 4275, 4004P, 4005P, 4007P, 4010P (trade name, manufactured by Mitsubishi Chemical Corporation).

An epoxy resin having an epoxy equivalent of 90 to 300 is preferable in that a synergistic effect of heat resistance of the resin can be obtained. The lower limit of the epoxy equivalent is more preferably 150, and still more preferably 170. The upper limit of the epoxy equivalent is more preferably 250, and still more preferably 230. As the epoxy resin having an epoxy equivalent of 90 to 300, it is preferable to use a resin which is solid at room temperature.

The epoxy resin having an epoxy equivalent of 90 to 300 is more preferably a novolak type epoxy resin. The novolak-type epoxy resin has good compatibility with other epoxy resins, and the difference in reactivity in the epoxy period is small even though the density of the epoxy resin is high, so that the entire coating film can be made uniformly in a high bridge density.

The novolak type epoxy resin is not particularly limited and examples thereof include cresol novolak type epoxy resin, phenol novolak type epoxy resin,? -Naphthol novolak type epoxy resin and brominated phenol novolak type epoxy resin.

Examples of commercially available epoxy resins usable as epoxy resins having an epoxy equivalent of 90 to 300 include EPICLON N-660, N-665, N-670, N-673, N-680, EXP-S, N-662-EXP-S, N-665-EXP, N-665-EXP-S, N-672-EXP, N-670- N-670-80M, N-680-75M, N-690-75M, N-740, N-770, N-775, N-740-80M, N-770-70M, N-865, N-865-80M 700, YDCN-700-3, YDCN-700-5, YDCN-700, YDCN-700, YDCN- 700-7, YDCN-700-10, YDCN-704, and YDCN-700-A (trade names, manufactured by Nippon Steel Chemical Co., Ltd.).

When the novolak type epoxy resin is used as the epoxy resin having an epoxy equivalent of 90 to 300, an epoxy resin other than the novolak type epoxy resin which is solid at ordinary temperature is used for the epoxy resin having an epoxy equivalent of 800 to 10000 . If the adhesive layer is made only of a novolak type epoxy resin, there is a problem in that the adhesiveness is not sufficient. Therefore, it is preferable to use an epoxy resin other than the novolak type epoxy resin as the epoxy resin having an epoxy equivalent of 800 to 10,000.

In the present invention, the ratio of the thermosetting resin having a functional group reactive with an epoxy group to the epoxy resin is preferably 50 to 500 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the thermosetting resin having a functional group reactive with the epoxy group , And more preferably 50 to 200 parts by mass in view of the adhesiveness after the main bonding. When the ratio is within the above range, the degree of crosslinking with the thermosetting resin having a functional group capable of reacting with the epoxy group is appropriately adjusted, so that the flexibility of the conductive adhesive composition or the electromagnetic shielding film and the adhesiveness to the printed wiring board are improved. Particularly, with respect to 100 parts by mass of the thermosetting resin having a functional group capable of reacting with the epoxy group, the flowability, adhesiveness after adhesion and adhesion with the resin plate are improved by an amount of 50 parts by mass or more, The adhesion to the metal material such as gold plating is improved.

<Conductive filler>

The conductive adhesive film of the present invention contains the conductive filler (H). The conductive filler (H) is not particularly limited, and for example, a metal filler, a metal-coated resin filler, a carbon filler, and a mixture thereof can be used. Examples of the metal filler include copper powder, silver powder, nickel powder, silver-coated copper powder, gold-coated copper powder, silver-coated nickel powder, and gold-coated nickel powder. These metal powders are used in electrolytic methods, atomization methods, .

Particularly, the average particle diameter of the conductive filler is preferably 3 to 50 占 퐉 so that the contact between the fillers can be easily obtained. Examples of the shape of the conductive filler include a spherical shape, a flake shape, a resin shape, and a fibrous shape.

The conductive filler (H) is preferably at least one selected from the group consisting of silver powder, silver-coated copper powder and copper powder from the viewpoint of connection resistance and cost.

The conductive filler (H) is preferably contained in an amount of 40 to 90 mass% with respect to the total amount of the conductive adhesive composition.

The conductive adhesive film may further contain a silane coupling agent, an antioxidant, a pigment, a dye, a tackifier resin, a plasticizer, an ultraviolet absorber, a defoamer, a leveling regulator, a filler, a flame retardant, etc. in such a range as not to deteriorate solder reflow resistance .

<Urethane resin particle>

The urethane resin particles (I) contained in the conductive adhesive composition of the present invention preferably have an average particle diameter of from 4 탆 to 13 탆, and preferably from 5 탆 to 7 탆.

The term &quot; average particle size &quot; as used herein refers to a particle size distribution measuring apparatus (Nikotec (registered trademark) particle size distribution measuring apparatus UPA-EX150 ) And the like.

The urethane resin particle (I) of the present invention has a hardness (A type durometer hardness) measured by an A type durometer in accordance with JIS K 6253 in the range of 55 to 90 inclusive. This is because if the hardness is less than 55, the flowability may be insufficient, and if the hardness is more than 90, the adhesion strength may become insufficient.

Thus, in the conductive adhesive composition of the present invention, the average particle diameter of the urethane resin particles (I) is set to 4 탆 or more and 13 탆 or less and the hardness of the urethane resin particles (I) is set to 55 or more and 90 or less, It is possible to obtain a conductive adhesive composition having excellent conductivity and excellent adhesiveness to a printed wiring board.

The blending amount of the urethane resin particles (I) relative to the total amount of the conductive adhesive composition is preferably 3 to 30 mass%. This is because when the compounding amount is less than 3 mass% and the compounding amount is more than 10 mass%, the connection resistance value may become unstable.

<Curing agent>

The conductive adhesive film of the present invention may contain a curing agent if necessary. The curing agent is not particularly limited and includes, for example, an isocyanate compound, a blocked isocyanate compound, a carbodiimide compound, an oxazoline compound, a melamine, and a metal complex system crosslinking agent Conventionally known curing agents may be used.

As the isocyanate compound, for example, toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl- Phenylenediisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4- (MDI), dirylene diisocyanate, tolyldinedisocyanate, xylylene diisocyanate (XDI), naphthalene diisocyanate (XDI), naphthalene diisocyanate Aromatic diisocyanates such as 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate bibenzyl; Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; ; 1,4-cyclohexylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophoronediisocyanate, hydrogen Aliphatic cyclic diisocyanates such as addition MDI and hydrogenated XDI; And polyurethane prepolymers obtained by reacting these diisocyanates with low molecular weight polyols or polyamines so that the terminals become isocyanates. The isocyanurate compounds of these isocyanate compounds , A burette, an adduct, a polymer, and the like, and conventionally known ones can be used, and there is no particular limitation.

As the above-mentioned block isocyanate compound, a compound obtained by blocking the above-mentioned isocyanate compound by a known method can be used. The blocking compound is not particularly limited, and phenol compounds such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam systems such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propiolactam; Active methylenes such as ethyl acetoacetate and acetylacetone; But are not limited to, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, t-butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono 2-ethylhexyl ether, Alcohols such as methyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate, and furfuryl alcohol; Oxime compounds such as formaldoxime, acetal decyl, acetoxime, methyl ethyl ketoxime, diacetyl monooxime and cyclohexane oxime; Mercaptan systems such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol and ethylthiophenol; Acid amides such as acetic acid amide, benzamide and the like; Imide systems such as succinic acid imide and maleic acid imide; Imidazole compounds such as imidazole and 2-ethylimidazole; Secondary amines such as dimethylamine, diethylamine and dibutylamine; And pyrazole such as pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

The carbodiimide compound is not particularly limited, and examples thereof include those obtained by the decarbonation condensation reaction of the above-described isocyanate compound.

The oxazoline compound is not particularly limited, and examples thereof include 2,2'-bis- (2-oxazoline), 2,2'-methylene-bis- (2-oxazoline) (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'-tetramethylene- Hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'- ethylene- bis- (4,4- ), 2,2 '- (1,3-phenylene) -bis- (2-oxazoline), 2,2' - (2-oxazoline), bis- (2-oxazolinylcyclohexane) sulfide, bis- (2-oxazolidinyl) Dioxazoline compounds such as norbornane) sulfide; Trioxazoline compounds such as 2,2 '- (1,2,4-phenylene) -tris- (2-oxazoline); And oxazoline group-containing polymers such as styrene-2-isopropenyl-2-oxazoline copolymer.

The appropriate amount of these curing agents is effective for improving heat resistance and the like. However, if the amount of the curing agent to be used is excessively large, the flexibility and the adhesiveness may be lowered. Therefore, the amount of the curing agent to be used is preferably 0.1 to 200 parts by mass, more preferably 0.2 to 100 parts by mass, per 100 parts by mass of the resin component of the thermosetting resin having a functional group reactive with an epoxy group.

In the conductive adhesive film of the present invention, an imidazole-based curing accelerator may be used in combination in order to accelerate curing of the curing agent. The curing accelerator is not particularly limited and examples thereof include 2-phenyl-4,5-dihydroxymethylimidazole, 2-heptadecylimidazole, 2,4-diamino-6- (2 ' 2-phenylimidazole, 5-cyano-2-phenylimidazole, 2,4-diamino-2-phenylimidazole, (2 ') - ethyl-S-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methyl Imidazole isocyanuric acid adduct, imidazole isocyanuric acid adduct, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methyl imidazole, Hydroxyl group, azine, and the like. These curing accelerators are effective for improving heat resistance and the like in a proper amount. However, when the amount of the curing accelerator to be used is excessively large, the flexibility and adhesion may be lowered. Therefore, the amount of the curing accelerator to be used is preferably 0.01 to 1.0 part by mass based on 100 parts by mass of the resin component of the thermosetting resin having a functional group reactive with an epoxy group.

&Lt; Conductive adhesive film &

As shown in Fig. 1, the conductive adhesive film 1 of the present invention is a conductive adhesive film comprising a releasable base material 2 (release film) and a conductive adhesive composition formed by coating the surface of the releasable base material 2 with the above- And an adhesive layer (4). The coating method is not particularly limited, and known coating equipment represented by a die coater, a lib coater, a comma coater, or the like can be used. The conditions for coating the releasable base material 2 with the conductive adhesive composition may be appropriately set.

The releasable base material 2 may be a base film such as polyethylene terephthalate or polyethylene naphthalate coated with a silicone or non-silicone release agent on the surface of the conductive adhesive layer 4 on which the conductive adhesive layer 4 is formed. Here, the thickness of the peelable base material 2 is not particularly limited, and is determined in consideration of the convenience of use.

The thickness of the conductive adhesive layer 4 is preferably 15 to 100 mu m. If it is thinner than 15 탆, the filling property becomes insufficient and sufficient connection with the ground circuit may not be obtained. If it is thicker than 100 탆, it is disadvantageous in terms of cost, and it becomes impossible to meet the demand for thinning. By setting the thickness to such a value, when the concavo-convex exists in the base material, it flows appropriately, so that it can be deformed into a shape to fill the concave portion and can be adhered with good adhesion.

<Anisotropic Conductive Adhesive Layer, Isotropic Conductive Adhesive Layer>

The conductive adhesive composition of the present invention can be used as an anisotropic conductive adhesive layer or an isotropic conductive adhesive layer depending on the purpose of use. For example, when the conductive adhesive composition of the present invention is used as a conductive adhesive film for bonding to a reinforcing plate, it can be used as an isotropic conductive adhesive layer.

In the case of an electromagnetic wave shielding film having a metal layer, it may be used as an isotropic conductive adhesive layer or an anisotropic conductive adhesive layer, but it is preferably used as an anisotropic conductive adhesive layer.

They may be an isotropic conductive adhesive layer or an anisotropic conductive adhesive layer depending on the blending amount of the conductive filler (H). In order to form the anisotropic conductive adhesive layer, it is preferable that the conductive filler is contained in the total solid content of the conductive adhesive composition at 5 mass% or more and less than 40 mass%. In order to form an isotropic conductive adhesive layer, it is preferable that the conductive filler (H) be at least 40 mass% and not more than 90 mass% in the total solid content of the conductive adhesive composition.

In addition, the conductive adhesive film using the conductive adhesive of the present invention is excellent in adhesion to a printed wiring board, and adhesion to the printed wiring board is improved by adhesion to a resin plate such as a polyimide film and adhesion of a gold- And adhesion to the same metal material.

<Electromagnetic wave shielding film>

2, the electromagnetic wave shielding film 20 using the conductive adhesive composition of the present invention has a conductive adhesive layer 4 and a protective layer 13 formed on the surface of the conductive adhesive layer 4. As shown in Fig. The protective layer 13 is not particularly limited as long as it has an insulating property (that is, one formed by an insulating resin composition), and known ones can be used. As the protective layer 13, a resin component (excluding a conductive filler) used in the above-described conductive adhesive layer 4 may be used. The protective layer 13 may be a laminate of two or more layers having different physical properties such as a material or hardness or elastic modulus.

The thickness of the protective layer 13 is not particularly limited and may be suitably set as necessary. However, the thickness of the protective layer 13 is preferably 1 占 퐉 or more (preferably 4 占 퐉 or more), 20 占 퐉 or less (preferably 10 占 퐉 or less, 5 mu m or less).

The protective layer 13 may also contain a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, a defoaming agent, a leveling agent, a filler, a flame retardant, a viscosity modifier, .

The electromagnetic wave shielding film 20 can be obtained by forming a protective layer 13 by coating a resin composition for a protective layer on one side of a peelable film and drying it and then forming a protective layer 13 on the protective layer 13 , And coating and drying the above-mentioned conductive adhesive composition to form the conductive adhesive layer (4).

Examples of the method for forming the conductive adhesive layer 4 and the protective layer 13 include a known coating method such as a gravure coating method, a kiss coating method, a die coating method, a lip coating method, a comma coating method, A coating method, a roll coating method, a knife coating method, a spray coating method, a bar coating method, a spin coating method and a dip coating method.

The electromagnetic wave shielding film 20 can be adhered to the printed wiring board by a hot press. The conductive adhesive layer 4 of the electromagnetic wave shielding film 20 is softened by heating and flows into the ground portion formed on the printed wiring board by pressing. As a result, the ground circuit and the conductive adhesive are electrically connected to each other to enhance the shielding effect.

The electromagnetic wave shielding film 20 can be used, for example, in the shielded printed wiring board 30 shown in Fig. The shielded printed wiring board 30 includes a printed wiring board 40 and an electromagnetic wave shielding film 20. [

The printed wiring board 40 includes a base substrate 41, a printed circuit (ground circuit) 42 formed on the base substrate 41, and an insulating adhesive layer 42 formed adjacent to the printed circuit 42 on the base substrate 41. [ An insulating adhesive layer 43, and an insulating coverlay 44 formed to cover the insulating adhesive layer 43. An insulating layer of the printed wiring board 40 is constituted by the insulating adhesive layer 43 and the coverlay 44. A part of the printed circuit 42 is exposed to the insulating adhesive layer 43 and the coverlay 44 The opening 45 is formed.

The base substrate 41, the insulating adhesive layer 43, and the coverlay 44 are not particularly limited and may be formed of, for example, a resin film or the like. In this case, it can be formed by a resin such as polypropylene, crosslinked polyethylene, polyester, polybenzimidazole, polyimide, polyimideamide, polyetherimide, or polyphenylene sulfide. The printed circuit 42 may be formed of, for example, a copper wiring pattern formed on the base substrate 41. [

Next, a method of manufacturing the shielded printed circuit board 30 will be described. The electromagnetic wave shielding film 20 is placed on the printed wiring board 40 and pressed while heating with a press machine. A part of the adhesive layer 4 softened by heating flows into the opening 45 by pressurization. As a result, the electromagnetic wave shielding film 20 is bonded to the printed wiring board 40 via the adhesive layer 4.

<Electromagnetic Wave-Shielding Film Having Metal Layer>

The electromagnetic wave shielding film of the present invention may have a metal layer. By having a metal layer, more excellent electromagnetic wave shielding performance can be obtained.

More specifically, for example, as shown in Fig. 3, the electromagnetic wave shielding film 21 using the conductive adhesive composition of the present invention comprises a metal layer (shielding layer) 14, And a protective layer 13 formed on the second surface side opposite to the first surface of the metal layer 14. The conductive adhesive layer 4 is formed on the first surface of the metal layer 14,

Examples of the metal material for forming the metal layer 14 include nickel, copper, silver, tin, gold, palladium, aluminum, chromium, titanium, zinc, and alloys or the like containing any two or more of these materials And can be appropriately selected according to the required electromagnetic shielding effect and repeated bending and sliding resistance.

The thickness of the metal layer 14 is not particularly limited and may be set to, for example, 0.1 m to 8 m. Examples of the method for forming the metal layer 14 include an electrolytic plating method, an electroless plating method, a sputtering method, an electron beam evaporation method, a vacuum evaporation method, a CVD method, and an organic metal method. The metal layer 14 may be a metal foil or metal nano-particles.

The electromagnetic wave shielding film 21 can be used for the shielded printed circuit board 31 shown in Fig. 3, for example. The shielded printed circuit board 31 includes the printed wiring board 40 and the electromagnetic wave shielding film 21 described above.

Next, a method of manufacturing the shielded printed circuit board 31 will be described. The electromagnetic wave shielding film 21 is placed on the printed wiring board 40 and pressed while heating with a press machine. A part of the adhesive layer 4 softened by heating flows into the opening 45 by pressurization. The electromagnetic wave shielding film 21 is bonded to the printed wiring board 40 via the adhesive layer 4 and the metal layer 14 and the printed circuit 42 of the printed wiring board 40 are connected via the conductive adhesive And the metal layer 14 and the printed circuit 42 are connected.

<Shielded Printed Circuit Board Having a Gusset>

Further, the conductive adhesive composition of the present invention can be used for a shielded printed wiring board having a reinforcing plate. More specifically, it can be used, for example, in the shielded printed wiring board 32 shown in Fig. The shielded printed circuit board 32 includes a printed wiring board 47, a conductive adhesive layer 4, and a conductive reinforcing plate 15. The printed wiring board 47 and the conductive reinforcing plate 15 are bonded and electrically connected by the conductive adhesive layer 4 of the present invention.

In the printed wiring board 47, a plating layer (for example, a gold-plated layer) 46 is formed on a part of the surface of the printed circuit 42, and the plating layer 46 is exposed from the opening 45.

2, the printed circuit 42 and the conductive reinforcing plate 42 are bonded to each other through the adhesive layer 4 that has flowed into the opening 45 without forming the plating layer 46. Further, in the same manner as the shielded printed circuit board 30 shown in Fig. (15) may be directly connected.

The conductive reinforcing plate 15 is formed in the printed wiring board on which the electronic components are mounted to prevent the electronic parts from being damaged due to deformation in the area where the electronic parts are mounted due to bending of the printed wiring board. As the conductive reinforcing plate 15, a conductive metal plate or the like can be used. For example, a stainless steel plate, an iron plate, a copper plate, an aluminum plate, or the like can be used. Of these, it is more preferable to use a stainless steel plate. By using the stainless steel plate, even if the plate thickness is thin, it has sufficient strength to support the electronic part.

The thickness of the conductive reinforcing plate 15 is not particularly limited, but is preferably 0.025 to 2 mm, more preferably 0.1 to 0.5 mm. When the thickness of the conductive reinforcing plate 15 is within this range, the circuit board to which the conductive reinforcing plate 15 is adhered can be easily accommodated in a small apparatus and has sufficient strength to support the mounted electronic component . On the surface of the conductive reinforcing plate 15, a metal layer such as Ni or Au may be formed by plating or the like. The surface of the conductive reinforcing plate 15 may be provided with a concavo-convex shape by sandblasting, etching, or the like.

Examples of electronic components include chip components such as resistors and capacitors in addition to connectors and ICs.

Next, a method of manufacturing the shielded printed circuit board 32 will be described. First, a conductive adhesive film to be a conductive adhesive layer 4 is placed on the conductive reinforcing plate 15 and pressed while heating with a press machine to produce a conductive adhesive film having a reinforcing plate. Next, a conductive adhesive film having a reinforcing plate is placed on the printed wiring board 47 and pressed while heating with a press machine. A part of the adhesive layer 4 softened by heating flows into the opening 45 by pressurization. As a result, the conductive reinforcing plate 15 is bonded to the printed wiring board 47 via the adhesive layer 4, and the conductive reinforcing plate 15 and the printed circuit 42 of the printed wiring board 47 are bonded to each other via the conductive adhesive And the conductive reinforcing plate 15 and the printed circuit 42 are brought into a conductive state. Therefore, the electromagnetic shielding performance by the conductive reinforcing plate 15 can be obtained.

As an adherend to which the conductive adhesive film formed by the conductive adhesive composition of the present invention can be adhered, for example, a flexible wiring board which is repeatedly bent can be given as a representative example, but it is also applicable to a rigid printed wiring board Of course it is. Further, the present invention is applicable not only to the single-sided shielding wiring board but also to the double-sided shielding wiring board.

Example

Hereinafter, the present invention will be described on the basis of examples. Here, the present invention is not limited to these examples, and these examples can be modified or changed based on the object of the present invention, and they are not excluded from the scope of the invention.

(Examples 1 to 6 and Comparative Examples 1 to 5)

&Lt; Preparation of conductive adhesive film &

The conductive adhesive films of Examples 1 to 6 and Comparative Examples 1 to 5 having the composition (mass%) shown in Table 1 were produced by the following production methods.

Each of the materials shown in Table 1 was blended to prepare a paste-like conductive adhesive composition. Here, as a thermosetting resin having a functional group capable of reacting with an epoxy group, a mixture of 35 parts by mass of a polyurethane polyurea resin having an acid value of 2 and 45 parts by mass of a polyurethane polyurea resin having an acid value of 26 was used and a phenoxy type epoxy resin 20 parts by mass of phenol novolac epoxy resin (product of Mitsubishi Chemical Corporation, trade name: jER152), 20 parts by mass of a rubber-modified epoxy resin (trade name: ERP-4030, manufactured by Adeka Corporation) , DURANATE 17B-60PX (manufactured by Asahi Kasei Corporation) was used as a block isocyanate curing agent, and 2MA-OK (manufactured by Shikoku Chemicals Corporation) was used as an imidazole series curing accelerator. Urethane beads (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., trade name: DIAMIC BEAZ) were used as the urethane resin particles. As the silica particles, Sylysia 360 (manufactured by Fuji Silysia Chemical Ltd., average particle diameter: 5 탆) was used.

Next, the conductive adhesive composition thus prepared was hand-coated on a polyethylene terephthalate film (separate film) subjected to release treatment using a doctor blade (plate-shaped blade) and dried at 100 占 폚 for 3 minutes to obtain a conductive adhesive film Respectively. Also, the doctor blade was suitably selected from 1 mil to 5 mil products (1 mil = 1/1000 inches = 25.4 占 퐉), depending on the thickness of the conductive adhesive film to be produced. In each of the Examples and Comparative Examples, each of the conductive adhesive films was formed so as to have a predetermined thickness shown in Table 1. [ The thickness of the conductive adhesive film was measured in terms of micrometer.

(Example 7)

Each of the materials shown in Table 1 was blended to prepare a paste-like conductive adhesive composition. 83 parts by mass of a carboxyl group-modified polyester resin (number average molecular weight: 15000, Tg: 15 占 폚) having an acid value of 12 mgKOH / g was used as the thermosetting resin and a cresol novolak epoxy resin (epoxy equivalent: 220 g / , Tg: 90 占 폚). As urethane resin particles, 10 parts by mass of urethane beads having an average particle diameter of 7 탆 and a hardness of 74 were used.

Next, a conductive adhesive film was produced in the same manner as in Example 1.

(Examples 8 to 13)

A paste-like conductive adhesive composition and a conductive adhesive film were prepared in the same manner as in Example 7, except that the acid value and blending amount of the carboxyl group-modified polyamide resin, the blending amount of the epoxy resin, and the hardness of the urethane resin particles were changed as shown in Table 2 Respectively.

(Comparative Example 6)

A paste-like conductive adhesive composition and a conductive adhesive film were prepared in the same manner as in Example 7 except that silica particles having an average particle size of 4 占 퐉 (manufactured by Fuji Silysia Chemical Ltd., trade name: Sylysia 350) were used instead of the urethane resin particles.

(Comparative Example 7)

Except that the acid value and blending amount of the carboxyl group modified polyester resin and the blending amount of the epoxy resin were changed as shown in Table 2 and the urethane resin was not used, the paste-like conductive adhesive composition and the conductive adhesive A film was produced.

(Example 14)

Each of the materials shown in Table 3 was compounded to prepare a paste-like conductive adhesive composition. 71 parts by mass of a carboxyl group-modified polyamide resin (number average molecular weight: 2000, Tg: 30 占 폚) having an acid value of 18 mgKOH / g was used as the thermosetting resin, and 40 parts by mass of a cresol novolak type epoxy resin 10 g / eq) / mixed resin of bisphenol A type epoxy resin (liquid at normal temperature, equivalent: 250 g / eq) = 90/10% As urethane resin particles, 19 parts by mass of urethane beads having an average particle diameter of 7 탆 and a hardness of 58 were used.

Next, in the same manner as in Example 1, a conductive adhesive film was produced.

(Examples 15 to 16)

A paste-like conductive adhesive composition and a conductive adhesive film were prepared in the same manner as in Example 14, except that the average particle diameter and hardness of the urethane resin particles were changed as shown in Table 3.

(Comparative Example 8)

Except that the blending amount of the carboxyl group-modified polyamide resin and the blending amount of the mixed resin of the cresol novolak type epoxy resin / bisphenol A type epoxy resin were changed as shown in Table 3, and the urethane resin particles were not used, , A paste-like conductive adhesive composition and a conductive adhesive film were prepared.

(Comparative Example 9)

A paste-like conductive adhesive composition and a conductive adhesive film were prepared in the same manner as in Example 14 except that silica particles having an average particle size of 4 占 퐉 (manufactured by Fuji Silysia Chemical Ltd., trade name: Sylysia 350) were used instead of the urethane resin particles.

[Table 1]

[Table 2]

[Table 3]

<Peeling strength measurement>

Next, the adhesion between the gold plating formed on the copper foil surface of the copper clad laminate and the conductive adhesive was measured by a 90 deg. Peel test. More specifically, the conductive adhesive film produced in Examples 1 to 16 and Comparative Examples 1 to 9 and the SUS plate metal reinforcing plate (thickness: 200 mu m) were pressed at a temperature of 170 DEG C for 3 minutes, The film was heated and pressed under the conditions of a pressure of 2 Mpa and further heated at 150 캜 for one hour, and then the separator film was peeled off to produce a conductive adhesive film having a metal reinforcing plate.

Then, a conductive adhesive film comprising a base substrate made of polyimide, a copper foil formed on the surface of the base substrate, a gold plating layer of a copper foil laminated film having a gold plating layer formed on the copper foil surface, and a metal reinforcing plate, The laminate was adhered under the same conditions as the thermocompression bonding, and then further adhered under the conditions of a temperature of 170 캜, a time of 30 minutes and a pressure of 3 Mpa by a press machine to produce a copper foil laminated film having a metal reinforcing plate. Then, the copper foil laminated film was peeled off at a room temperature by a tensile tester (product name: AGS-X50S, manufactured by Shimadzu Corporation) at a tensile rate of 50 mm / min and a peeling angle of 90 deg. Here, when the peel strength was 9.5 N / cm or more, the adhesion was evaluated to be excellent. Table 4 and Table 5 show the above results.

&Lt; Fabrication of circuit board with metal reinforcing plate >

Next, the conductive adhesive film (including the separator film) produced in Examples 1 to 16 and Comparative Examples 1 to 9 and the metal reinforcing plate (Ni plating the surface of the SUS plate, thickness: 200 m) Under the conditions of a temperature of 120 占 폚, a time of 5 seconds, and a pressure of 0.5 Mpa to prepare a conductive adhesive film having a metal reinforcing plate. Next, the separable film on the conductive adhesive film was peeled off, and the conductive adhesive film having the metal reinforcing plate was adhered to the flexible substrate under the same conditions as the thermocompression bonding. Thereafter, the temperature was maintained at 170 ° C for 30 minutes, 3Mpa to prepare a circuit board having a metal reinforcing plate. 5, a copper foil pattern 23 in which a gold plated layer 22 is formed on a part of the surface is formed on a polyimide film 29, and a copper foil pattern 23 made of a polyimide film is formed thereon. A coverlay 24 was formed. Then, a conductive adhesive film 25 provided with a metal reinforcing plate 26 was adhered to the flexible substrate to produce a circuit board having a metal reinforcing plate. Here, an opening 27 having a ground connection portion with a diameter of 0.8 mm was formed in the coverlay 24.

<Measurement of connection resistance value>

Next, as shown in Fig. 6, in the circuit board provided with the metal reinforcing plate fabricated in Examples 1 to 16 and Comparative Examples 1 to 9, two copper foil patterns 23 having gold plating layer 22 formed thereon, The electrical resistance value between the copper foil pattern 23 and the metal reinforcing plate 26 was measured by an ohmmeter 28 to evaluate the connectivity. Here, when the connection resistance is less than 0.1 ?, it is evaluated that the conductivity is excellent. Table 4 and Table 5 show the above results.

&Lt; Evaluation of flowability &

Next, the underflow performance of the copper foil laminated film (or the circuit board provided with the metal reinforcing plate) having the manufactured metal reinforcing plate was evaluated. As a reflow condition, a lead-free solder was assumed, and a temperature profile was set so that the polyimide film of the copper foil laminated film (or the circuit board having the metal reinforcing plate) provided with the metal reinforcing plate was treated at 265 캜 for 5 seconds .

Then, after the copper foil laminated film having the metal reinforcing plates prepared in Examples 1 to 16 and Comparative Examples 1 to 9 was passed through hot air reflow three times, the peel strength at break after reflow The maximum value was measured. Here, when the peel strength was 9.5 N / cm or more, it was evaluated that the adhesion after reflow was excellent. Table 4 and Table 5 show the above results.

Further, after a circuit board having the metal reinforcing plates prepared in Examples 1 to 16 and Comparative Examples 1 to 9 was passed through hot air reflow once, three times, and five times, after the reflow was performed by the above- The connection resistance value was measured. Here, when the connection resistance was less than 0.1 Ω, it was evaluated that the conductivity was excellent after the reflow. Table 4 and Table 5 show the above results.

[Table 4]

[Table 5]

As shown in Tables 4 to 5, Examples 1 to 16 using urethane beads having an average particle diameter of 4 탆 or more and 13 탆 or less and a hardness of 55 or more and 90 or less exhibited excellent conductivity before and after reflow, It can be said that the adhesion to the film is excellent.

On the other hand, in Comparative Example 1 in which the average particle diameter of the urethane beads was small (i.e., 3 탆), the connection resistance did not sufficiently decrease before and after the reflow as in Comparative Examples 5 and 7 to 8 in which the urethane beads were not used.

In Comparative Example 2 in which the average particle diameter of the urethane beads was large (i.e., 15 占 퐉) and Comparative Example 3 in which the hardness of the urethane beads was large (that is, 95), the adhesiveness (before reflow) with the copper foil laminated film was insufficient .

Further, in Comparative Example 4 using silica particles (average particle diameter: 5 占 퐉) instead of urethane beads, the adhesion property (before reflow) with the copper foil laminated film is insufficient.

Further, in Comparative Example 6 using silica particles (average particle diameter: 4 占 퐉) instead of urethane beads, adhesion (after reflow) with the copper foil laminated film is insufficient.

Further, in Comparative Example 9 using silica particles (average particle diameter: 4 占 퐉) instead of urethane beads, adhesion (after reflow) with the copper foil laminated film is insufficient.

[Industrial applicability]

INDUSTRIAL APPLICABILITY As described above, the present invention is suitable for a conductive adhesive composition used in a printed wiring board.

1: Conductive adhesive film 2: Peelable substrate
4: Conductive adhesive layer 13: Protective layer
14: metal layer 15: conductive reinforcing plate
20, 21: electromagnetic wave shielding film
30, 31, 32: shielded printed circuit board
40, 47: printed wiring board 41: base substrate
42: Printed circuit 43: Insulating adhesive layer
44: Coverlay 45: Opening

Claims (6)

1. A conductive adhesive composition comprising a thermosetting resin having a functional group capable of reacting with an epoxy group, an epoxy resin, and a conductive filler,
(A) having an average particle diameter of not less than 4 mu m and not more than 13 mu m and having a durometer hardness of 55 or more and 90 or less as measured according to JIS K 6253. The conductive adhesive composition according to claim 1, The method according to claim 1,
Wherein the blending amount of the urethane resin particles with respect to the total amount of the conductive adhesive composition is 3 to 30 mass%. 3. The method according to claim 1 or 2,
Wherein the thermosetting resin is one selected from the group consisting of a carboxyl group modified polyester resin, a carboxyl group modified polyamide resin, and a carboxyl group modified polyurethane polyurea resin. A conductive adhesive film comprising a peelable base material and a conductive adhesive layer formed on the surface of the releasable base material and comprising the conductive adhesive composition according to any one of claims 1 to 3. An electromagnetic wave shielding film comprising: a protective layer having insulating properties; and a conductive adhesive layer formed on the surface of the protective layer, the conductive adhesive layer comprising the conductive adhesive composition according to claim 1 or 2. A base substrate on which a printed circuit is formed, a conductive adhesive layer made of the conductive adhesive composition according to claim 1 or 2, and a conductive reinforcing plate,
Wherein the base substrate and the conductive reinforcing plate are electrically connected by the conductive adhesive layer.

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